A subject-matter of the present invention is a cleaning or rinsing composition intended for the treatment of industrial, domestic or communal hard surfaces, in particular of glass, window, ceramic, tiling, hard organic polymer, metal or wood type and the like, targeted at conferring on the latter hydrophilic properties and properties of protection (corrosion resistance) of glass, of dishes and of designs by washing media during repeated washing operations in an automatic dishwasher.
A more particular subject-matter of the invention is a cleaning composition intended for the treatment of a hard surface which is capable of conferring persistent hydrophilic properties on the latter, so as to prevent the subsequent presence of marks due in particular to the drying of drops of water deposited on said surface.
Commercial detergent formulations make it possible to efficiently clean industrial, domestic or communal hard surfaces. They are generally composed of an aqueous solution of surfactants, in particular of nonionic and anionic surfactants, of alcohol(s), in order to facilitate drying, and optionally of sequestering agents and of bases, in order to adjust the pH. A significant failing in these detergent formulations is that subsequent contact of the hard surface with water can result in the presence of marks during drying. This contact with water after application of detergent can originate, for example, from rainwater, in the case of windows, from mains water on bathroom tiling, or from rinsing water when the cleaning requires rinsing. It can also originate from the drying of the dishes in the open air, in the case of detergent formulae for cleaning dishes by hand, or from the drying of dishes in an automatic device when the detergent is intended for a dishwasher. In the case of the cleaning of dishes in an automatic device, said formula can either be used in the cleaning cycle (detergent formula) or during the rinsing (rinsing liquid).
The presence of marks or stains left on the hard surfaces by the water coming into contact with the latter is due to the phenomenon of contraction of the water drops on contact with the hard surface, which, during subsequent drying, leave marks on the surface which reproduce the original shapes and sizes of the drops.
Until now, no satisfactory solution to this problem existed.
To solve the problem posed by the retraction and the drying of the drops of water, the solution consists in increasing the hydrophilicity of the surface in order to obtain a contact angle between the hard surface to be treated and the drop of water which is as small as possible.
The studies of the Inventors which have led to the present invention have made it possible to determine that this problem can be solved in an efficient and lasting way by incorporating, in conventional cleaning compositions for hard surfaces, a water-soluble or water-dispersible organic polymer compound having both a function of interaction with the surface to be treated and a function conferring a hydrophilic nature on this surface.
A first subject-matter of the invention is a cleaning or rinsing composition comprising at least one water-soluble or water-dispersible copolymer comprising, in the form of polymerized units:
(a) at least one monomer compound of general formula I: 
xe2x80x83in which
R1 is a hydrogen atom or a methyl or ethyl group;
R2, R3, R4, R5 and R6, which are identical or different, are linear or branched C1-C6, preferably C1-C4, alkyl, hydroxyalkyl or aminoalkyl groups;
m is an integer from 0 to 10, preferably from 0 to 2;
n is an integer from 1 to 6, preferably 2 to 4;
Z represents a xe2x80x94C(O)Oxe2x80x94 or xe2x80x94C(O)NHxe2x80x94 group or an oxygen atom;
A represents a (CH2)p group, p being an integer from 1 to 6, preferably from 2 to 4;
B represents a linear or branched C2-C12, advantageously C3-C6, polymethylene chain optionally interrupted by one or more heteroatoms or heterogroups, in particular O or NH, and optionally substituted by one or more hydroxyl or amino groups, preferably hydroxyl groups;
X, which are identical or different, represent counterions;
(b) at least one hydrophilic monomer carrying a functional group with an acidic nature which is copolymerizable with (a) and which is capable of being ionized in the application medium;
(c) optionally at least one monomer compound with ethylenic unsaturation with a neutral charge which is copolymerizable with (a) and (b), preferably a hydrophilic monomer compound with ethylenic unsaturation with a neutral charge, carrying one or more hydrophilic groups, which is copolymerizable with (a) and (b).
The monomer (a) can be prepared, for example, according to the following reaction schemes: 
The monomer (a) confers, on the copolymer, characteristics of interaction with the surface to be treated, making possible in particular anchoring of the copolymer to this surface.
The monomer (b) and optionally the monomer (c) confers hydrophilic characteristics on the copolymer which, after anchoring of the copolymer to the surface to be treated, are passed on to the surface.
This property of rendering the surface hydrophilic furthermore makes it possible to reduce the formation of condensation on the surface; this advantage can be made use of in cleaning formulae for windows and mirrors, in particular in bathrooms.
The copolymer according to the invention advantageously exhibits a molecular mass of at least 1000, advantageously of at least 10,000; it can range up to 20,000,000, advantageously up to 10,000,000.
Except when otherwise indicated, when the term molecular mass is used, it will refer to the weight-average molecular mass, expressed in g/mol. The latter can be determined by aqueous gel permeation chromatography (GPC) or measurement of the intrinsic viscosity in a 1N NaNO3 solution at 30xc2x0 C.
The copolymer is preferably a random copolymer.
Preferably, in the general formula (I) of the monomer (a),
Z represents C(O)O, C(O)NH or O, very preferably C(O)NH;
n is equal to 2 or 3, very particularly 3;
m ranges from 0 to 2 and is preferably equal to 0 or 1, very particularly to 0;
B represents 
xe2x80x83with q from 1 to 4, preferably equal to 1;
R1 to R6, which are identical or different, represent a methyl or ethyl group.
The preferred monomer (a) is Diquat of following formula: 
Xxe2x88x92 representing the chloride ion.
Other particularly advantageous monomers (a) are: 
The X anions are in particular a halogen, preferably chlorine, sulfonate, sulfate, hydrogensulfate, phosphate, phosphonate, citrate, formate and acetate anion.
The monomers (b) are advantageously C3-C8 carboxylic, sulfonic, sulfuric, phosphonic or phosphoric acids with monoethylenic unsaturation, their anhydrides and their salts which are soluble in water.
Mention may be made, among the preferred monomers (b), of acrylic acid, methacrylic acid, xcex1-ethacrylic acid, xcex2,xcex2-dimethylacrylic acid, methylenemalonic acid, vinylacetic acid, allylacetic acid, ethylidineacetic acid, propylidineacetic acid, crotonic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid, mesaconic acid, N-(methacroyl)alanine, N-(acryloyl)hydroxyglycine, sulfopropyl acrylate, sulfoethyl acrylate, sulfoethyl methacrylate, styrenesulfonic acid, vinylsulfonic acid, vinylphosphonic acid, phosphoethyl acrylate, phophonoethyl acrylate, phosphopropyl acrylate, phophonopropyl acrylate, phosphoethyl methacrylate, phophonoethyl methacrylate, phosphopropyl methacrylate, phophonopropyl methacrylate and the alkali metal and ammonium salts thereof.
Mention may be made, among the monomers (c), of acrylamide, vinyl alcohol, C1-C4 alkyl esters of acrylic acid and of methacrylic acid, C1-C4 hydroxyalkyl esters of acrylic acid and of methacrylic acid, in particular ethylene glycol and propylene glycol acrylate and methacrylate, polyalkoxylated esters of acrylic acid and of methacrylic acid, in particular the polyethylene glycol and polypropylene glycol esters, esters of acrylic acid or of methacrylic acid and of polyethylene glycol or polypropylene glycol C1-C25 monoalkyl ethers, vinyl acetate, vinylpyrrolidone or methyl vinyl ether.
The level of monomers (a) is advantageously between 3 and 80 mol %, preferably 10 to 60 mol %.
The level of monomers (b) is advantageously between 10 and 95 mol %, preferably 20 to 70 mol %.
The level of monomers (c) is advantageously between 0 and 50%, preferably 0 and 30%, very particularly from 5 to 25 mol %.
The molar ratio of cationic monomer to the anionic monomer (a)/(b) is advantageously between 80/20 and 5/95, preferably between 60/40 and 20/80.
The copolymers of the invention can be obtained according to known techniques for the preparation of copolymers, in particular by polymerization by the radical route of the starting ethylenically unsaturated monomers, which are known compounds or compounds which can be easily obtained by a person skilled in the art by employing conventional synthetic processes of organic chemistry.
Reference may in particular be made to the processes disclosed in U.S. Pat. No. 4,387,017 and EP 156,646.
The radical polymerization is preferably carried out in an environment which is devoid of oxygen, for example in the presence of an inert gas (helium, argon, and the like) or of nitrogen. The reaction is carried out in an inert solvent, preferably ethanol or methanol, and more preferably in water.
The polymerization is initiated by addition of a polymerization initiator. The initiators used are the free radical initiators commonly used in the art. Examples comprise organic peresters (t-butylperoxy pivalate, t-amylperoxy pivalate, t-butylperoxy xcex1-ethylhexanoate, and the like); organic compounds of azo type, for example azobisamidinopropane hydrochloride, azobisisobutyronitrile, azobis(2,4-dimethylvaleronitrile), and the like); inorganic and organic peroxides, for example hydrogen peroxide, benzyl peroxide and butyl peroxide, and the like; redox initiating systems, for example those comprising oxidizing agents, such as persulfates (in particular ammonium or alkali metal persulfates, and the like); chlorates and bromates (including inorganic or organic chlorates and/or bromates); reducing agents, such as sulfites and bisulfites (including inorganic and/or organic sulfites or bisulfites); oxalic acid and ascorbic acid, as well as the mixtures of two or more of these compounds.
The preferred initiators are water-soluble initiators. Sodium persulfate and azobisamidinopropane hydrochloride are in particular preferred.
In an alternative form, the polymerization can be initiated by irradiation using ultraviolet light. The amount of initiators used is generally an amount sufficient can produce initiation of the polymerization. The initiators are preferably present in an amount ranging from 0.001 to approximately 10% by weight with respect to the total weight of the monomers and are preferably in an amount of less than 0.5% by weight with respect to the total weight of the monomers, a preferred amount being situated in the range from 0.005 to 0.5% by weight with respect to the total weight of the monomers. The initiator is added to the polymerization mixture either continuously or noncontinuously.
When it is wished to obtain copolymers of high molecular mass, it is desirable to add fresh initiator during the polymerization reaction. The gradual or noncontinuous addition also makes possible a more efficient polymerization and a shorter reaction time. The polymerization is carried out under reaction conditions which are effective in polymerizing the monomers (a), the monomers (b) and optionally the monomers (c) under an atmosphere devoid of oxygen. The reaction is preferably carried out at a temperature ranging from approximately 30xc2x0 to approximately 100xc2x0 and preferably between 60xc2x0 and 90xc2x0 C. The atmosphere which is devoid of oxygen is maintained throughout the duration of the reaction, for example by maintaining a nitrogen flow throughout the reaction.
A particularly preferred copolymer is the following: 
with x having a mean value of 0 to 50%, preferably of 0 to 30%, very particularly of 5 to 25%,
y having a mean value of 10 to 95%, preferably of 20 to 70%,
z having a mean value of 3 to 80%, preferably of 10 to 60%,
and the y/z ratio preferably being of the order of 4/1 to 1/2, with x+y+z=100%, x, y and z representing the mol % of units derived from acrylamide, acrylic acid (sodium salt) and from Diquat respectively.
Other preferred polymers are as follows: 
with x having a mean value of 0 to 50%, preferably of 0 to 30%, very particularly of 5 to 25%,
y having a mean value of 10 to 95%, preferably of 20 to 70%,
z having a mean value of 3 to 80%, preferably of 10 to 60%,
and the y/z ratio preferably being of the order of 4/1 to 1/2; 
with x having a mean value of 0 to 50%, preferably of 0 to 30%, very particularly of 5 to 25%,
y having a mean value of 10 to 95%, preferably of 20 to 70%,
z having a mean value of 3 to 80%, preferably of 10 to 60%,
and the y/z ratio preferably being of the order of 4/1 to 1/2; 
with x having a mean value of 0 to 50%, preferably of 0 to 30%, very particularly of 5 to 25%,
y having a mean value of 10 to 95%, preferably of 20 to 70%,
z having a mean value of 3 to 80%, preferably of 10 to 60%,
and the y/z ratio preferably being of the order of 4/1 to 1/2; 
with x having a mean value of 0 to 50%, preferably of 0 to 30%, very particularly of 5 to 25%,
y having a mean value of 10 to 95%, preferably of 20 to 70%,
z having a mean value of 3 to 80%, preferably of 10 to 60%,
and the y/z ratio preferably being of the order of 4/1 to 1/2; 
with x having a mean value of 0 to 50%, preferably of 0 to 30%, very particularly of 5 to 25%,
y having a mean value of 10 to 95%, preferably of 20 to 70%,
z having a mean value of 3 to 80%, preferably of 10 to 60%,
and the y/z ratio preferably being of the order of 4/1 to 1/2; 
with x having a mean value of 0 to 50%, preferably of 0 to 30%, very particularly of 5 to 25%,
y having a mean value of 10 to 95%, preferably of 20 to 70%,
z having a mean value of 3 to 80%, preferably of 10 to 60%,
and the y/z ratio preferably being of the order of 4/1 to 1/2.
The copolymers according to the invention can be used in particular in cleaning compositions for hard surfaces.
In the cleaning field, the copolymers of the invention are of use in conferring hydrophilization properties on surfaces to which they are applied, in particular in conferring persistent properties of resistance to stains or marks on surfaces.
In addition, they exhibit the property of preventing or of limiting the corrosion of glass, dishes and designs by washing media during repeated washing operations in an automatic dishwasher.
The term xe2x80x9cpersistent properties of resistance to marks or stainsxe2x80x9d is understood to mean that the treated surface retains these properties over time, including after subsequent contacts with water, whether rainwater, water from the supply system or rinsing water, which may or may not have rinsing products added.
Another subject-matter of the invention is the novel copolymers as defined above.
Said copolymer can be introduced into a cleaning or rinsing formulation intended for the treatment of hard surfaces at a content of between 0.0005% and 10%, preferably between 0.001 and 5%, by weight with respect to the total weight of the formulation, according to the concentration of active ingredients in the composition.
The composition according to the invention preferably comprises at least one surfactant. The latter is advantageously anionic and/or nonionic. It can also be cationic, amphoteric or zwitterionic.
The polymer of formula I/surfactant ratio by weight is advantageously between 1/2 and 1/100, advantageously 1/5 and 1/50.
Mention may in particular be made, among anionic surfactants, of soaps, such as salts of C8-C24 fatty acid, for example salts of fatty acids derived from copra and from tallow; alkylbenzenesulfonates, in particular alkylbenzenesulfonates with a linear C8-C13 alkyl, in which the alkyl group comprises from 10 to 16 carbon atoms, alcohol sulfates, ethoxylated alcohol suphates, hydroxyalkylsulfonates; alkyl sulfates and alkylsulfonates, in particular with a C12-C16 group, monoglyceride sulfates and condensates of fatty acid chloride with hydroxyalkylsulfonates.
Advantageous anionic surfactants are, in particular:
alkyl ester sulfonates of formula Rxe2x80x94CH(SO3M)xe2x80x94COORxe2x80x2, where R represents a C8-20, preferably C10-C16, alkyl radical, Rxe2x80x2 a C1-C6, preferably C1-C3, alkyl radical and M an alkali metal (sodium, potassium or lithium) cation, a substituted or unsubstituted ammonium (methyl-, dimethyl-, trimethyl- or tetramethylammonium, dimethylpiperidinium, and the like) cation or a cation derived from an alkanolamine (monoethanolamine, diethanolamine, triethanolamine, and the like). Mention may very particularly be made of methyl ester sulfonates in which the R radical is a C14-C16 radical;
alkyl sulfates of formula ROSO3M, where R represents a C6-C24, preferably C10-C18, alkyl or hydroxyalkyl radical, M representing a hydrogen atom or a cation with the same definition as above, and their ethoxylenated (EO) and/or propoxylenated (PO) derivatives, having on average from 0.5 to 30, preferably from 0.5 to 10, EO and/or PO units;
alkylamide sulfates of formula RCONHRxe2x80x2OSO3M where R represents a C2-C22, preferably C6-C20, alkyl radical, Rxe2x80x2 a C2-C3 alkyl radical, M representing a hydrogen atom or a cation with the same definition as above, and their ethoxylenated (EO) and/or propoxylenated (PO) derivatives having on average from 0.5 to 60 EO and/or PO units;
salts of saturated or unsaturated C8-C24, preferably C14-C20, fatty acids, C9-C20 alkylbenzenesulfonates, primary or secondary C8-C22 alkylsulfonates, alkylglycerolsulfonates, the sulfonated polycarboxylic acids disclosed in GB-A-1,082,179, paraffin sulfonates, N-acyl-N-alkyltaurates, alkyl phosphates, isethionates, alkylsuccinamates, alkyl sulfosuccinates, sulfosuccinate monoesters or diesters, N-acyl-sarcosinates, alkylglycoside sulfates, or polyethoxycarboxylates, the cation being an alkali metal (sodium, potassium or lithium), a substituted or unsubstituted ammonium residue (methyl-, dimethyl-, trimethyl- or tetramethylammonium, dimethylpiperidinium, and the like) or a residue derived from an alkanolamine (monoethanolamine, diethanolamine, triethanolamine, and the like);
alkyl or alkylaryl phosphate esters, such as Rhodafac RA600, Rhodafac PA15 or Rhodafac PA23, sold by the company Rhodia.
Mention may in particular be made, among nonionic surfactants, of condensates of alkylene oxide, in particular of ethylene oxide, with alcohols, polyols, alkylphenols, fatty acid esters, fatty acid amides and fatty amines; amine oxides, sugar derivatives, such as alkylpolyglycosides or fatty acid esters of sugars, in particular sucrose monopalmitate; long-chain tertiary phosphine oxides; dialkyl sulfoxides; block copolymers of polyoxyethylene and of polyoxypropylene; polyalkoxylated sorbitan esters; fatty esters of sorbitan, poly(ethylene oxide)s and fatty acid amides modified so as to give them a hydrophobic nature (for example, fatty acid mono- and diethanolamides comprising from 10 to 18 carbon atoms).
Mention may particularly be made of
polyoxyalkylenated (polyethoxyethylenated, polyoxypropylenated or polyoxybutylenated) alkylphenols in which the alkyl substituent is a C6-C12 alkyl substituent and which comprise from 5 to 25 oxyalkylene units; mention may be made, by way of example, of Triton X-45, X-114, X-100 or X-102, sold by Rohm and Haas Co.;
glucosamides, glucamides or glycerolamides;
polyoxyalkylenated C8-C22 aliphatic alcohols comprising from 1 to 25 oxyalkylene (oxyethylene, oxypropylene) units. Mention may be made, by way of example, of Tergitol 15-S-9 or Tergitol 24-L-6 NMW, sold by Union Carbide Corp., Neodol 45-9, Neodol 23-65, Neodol 45-7 or Neodol 45-4, sold by Shell Chemical Co., or Rhodasurf IDO60, Rhodasurf LA90 or Rhodasurf IT070, sold by the company Rhodia;
amine oxides, such as (C10-C18 alkyl)dimethylamine oxides or (C8-C22 alkoxy)ethyldihydroxyethylamine oxides;
the alkylpolyglycosides disclosed in U.S. Pat. No. 4,565,647;
C8-C20 fatty acid amides;
ethoxylated fatty acids;
ethoxylated amines.
Cationic surfactants are, in particular, alkylammonium salts of formula
R1R2R3R4N+Xxe2x88x92,
where
Xxe2x88x92 represents a halide, CH3SO4xe2x88x92 or C2H5SO4xe2x88x92 ion
R1 and R2 are alike or different and represent a C1-C20 alkyl radical or an aryl or benzyl radical
R3 and R4 are alike or different and represent a C1-C20 alkyl radical, an aryl or benzyl radical or an ethylene oxide and/or propylene oxide condensate (CH2CH2O)xxe2x80x94(CH2CHCH3O)yxe2x80x94H, where x and y range from 0 to 30 and are never simultaneously zero, such as cetyltrimethylammonium bromide, Rhodaquat(copyright) TFR, sold by the company Rhodia.
Examples of zwitterionic surfactants comprise aliphatic quaternary ammonium derivatives, in particular 3-(N,N-dimethyl-N-hexadecylammonio)propane-1-sulfonate and 3-(N,N-dimethyl-N-hexadecylammonio)-2-hydroxypropane-1-sulfonate.
Examples of amphoteric surfactants comprise betaines, sulfobetaines and carboxylates and sulfonates of fatty acids and of imidazole.
The following surfactants are preferred:
alkyl dimethyl betaines, alkyl amidopropyldimethyl betaines, alkyl dimethyl sulfobetaines or alkyl amidopropyldimethyl sulfobetaines, such as Mirataine CBS, sold by the company Rhodia, or the condensation products of fatty acids and of protein hydrolysates;
alkyl amphoacetates or alkyl amphodiacetates in which the alkyl group comprises from 6 to 20 carbon atoms;
amphoteric alkylpolyamine derivatives, such as Amphionic XL(copyright), sold by Rhodia, or Ampholac 7T/X(copyright) and Ampholac 7C/X(copyright), sold by Berol Nobel.
Additional examples of suitable surfactants are compounds generally used as surfactants denoted in the well-known texts xe2x80x9cSurface Active Agentsxe2x80x9d, volume I, by Schwartz and Perry, and xe2x80x9cSurface Active Agents and Detergentsxe2x80x9d, volume II, by Schwartz, Perry and Berch.
The surfactants can be present, if necessary, in a proportion of 0.005 to 60%, in particular of 0.5 to 40%, by weight, depending on the nature of the surfactant(s) and on the destination of the cleaning or rinsing composition.
Mention may be made, among the other common additives which are part of the formulation of detergent compositions, of:
In Particular for Washing in a Dishwasher
organic builders (detergency adjuvants which improve the surface properties of surfactants) of the type:
organic phosphonates, such as those of the Dequest(copyright) range from Monsanto (in a proportion of 0 to 2% of the total weight of detergent composition, expressed as dry matter, in the case of a dishwasher composition);
polycarboxylic acids or their water-soluble salts and water-soluble salts of carboxylic polymers or copolymers, such as
polycarboxylate or hydroxypolycarboxylate ethers
polyacetic acids or their salts (nitriloacetic acid, N,N-dicarboxymethyl-2-aminopentanedioic acid, ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, ethylenediaminetetraacetates, nitrilotriacetates, such as Nervanaid NTA Na3, sold by the company Rhodia, or N-(2-hydroxyethyl)nitrilodiacetates) (in a proportion of 0 to 10% of the total weight of the detergent composition, expressed as dry matter, in the case of a dishwasher composition);
(C5-C20 alkyl)succinic acid salts
polycarboxylic acetal esters
polyaspartic or polyglutamic acid salts
citric acid, gluconic acid or tartaric acid or their salts (in a proportion of 0 to 10% of the total weight of the detergent composition, expressed as dry matter, in the case of a dishwasher composition);
inorganic builders (detergency adjuvants which improve the surface properties of surfactants) of the type:
alkali metal, ammonium or alkanolamine polyphosphates, such as Rhodiaphos HPA3.5, sold by the company Rhodia (in a proportion of 0 to 70% of the total weight of the detergent composition, expressed as dry matter, in the case of a dishwasher composition);
alkali metal pyrophosphates;
zeolites;
silicates (in an amount which can range up to approximately 50% of the total weight of said detergent composition, expressed as dry matter, in the case of a dishwasher composition);
alkali metal or alkaline earth metal borates, carbonates, bicarbonates or sesquicarbonates (in an amount which can range up to approximately 50% of the total weight of said detergent composition, expressed as dry matter, in the case of a dishwasher composition);
cogranules of alkali metal (sodium or potassium) silicate hydrates and of alkali metal (sodium or potassium) carbonates disclosed in EP-A-488,868, such as Nabion 15, sold by the company Rhodia (in an amount which can range up to approximately 50% of the total weight of said detergent composition, expressed as dry matter, in the case of a dishwasher composition);
(it being possible for the total amount of organic and/or inorganic builders to represent up to 90% of the total weight of said detergent composition, expressed as dry matter, in the case of a dishwasher composition);
bleaching agents of the perborates or percarbonates type, which may or may not be combined with acetylated bleaching activators, such as N,N,Nxe2x80x2,Nxe2x80x2-tetraacetylethylenediamine (TAED), or chlorinated products of the chloroisocyanurates type, or chlorinated products of the alkali metal hypochlorites type (in a proportion of 0 to 30% of the total weight of said detergent composition, expressed as dry matter, in the case of a dishwasher composition);
auxiliary cleaning agents of the copolymers of acrylic acid and of maleic anhydride or acrylic acid homopolymers type (in a proportion of 0 to 10% of the total weight of said detergent composition, expressed as dry matter, in the case of a dishwasher composition);
fillers of the sodium sulfate or sodium chloride type, in a proportion of 0 to 50% of the total weight of said composition, expressed as dry matter;
various other additives, such as agents which influence the pH of the detergent composition, in particular basifying additives which are soluble in the washing medium (phosphates of alkali metals, carbonates, perborates or hydroxides or acidifying additives which are soluble in the washing medium (carboxylic or polycarboxylic acids, alkali metal bicarbonates and sesquicarbonates, phosphoric and polyphosphoric acids, sulfonic acids, and the like); or enzymes or fragrances, dyes or inhibitors of metal corrosion;
In Particular for Washing Dishes by Hand
synthetic cationic polymers, such as Mirapol A550(copyright) or Mirapol A15(copyright), sold by Rhodia, or Merquat 550(copyright), sold by Calgon;
polymers used to control the viscosity of the mixture and/or the stability of the foams formed during use, such as cellulose derivatives or guar derivatives (carboxymethylcellulose, hydroxyethylcellulose, hydroxypropylguar, carboxymethylguar, carboxymethylhydroxypropylguar, and the like);
hydrotropic agents, such as short-chain C2-C8 alcohols, in particular ethanol, diols and glycols, such as diethylene glycol, dipropylene glycol, and the like;
hydrating or moisturizing agents for the skin, such as glycerol or urea, or agents for protecting the skin, such as proteins or protein hydrolysates, or cationic polymers, such as cationic guar derivatives (Jaguar C13S(copyright), Jaguar C162(copyright) or Hicare 1000(copyright), sold by the company Rhodia.
The compositions according to the invention can be diluted (in water) from 1- to 10,000-fold, preferably from 1- to 1000-fold, before use.
The cleaning composition according to the invention is applied to the surface to be treated in an amount such that it allows, after rinsing, if necessary, and after drying, a deposit of copolymer according to the invention of 0.0001 to 1 g/m2, preferably 0.001 to 0.1 g/m2, of surface to be treated.
According to a particularly advantageous form, the cleaning composition according to the invention is employed for the treatment of glass surfaces, in particular windows. This treatment can be carried out by the various known techniques. Mention may be made in particular of the techniques for cleaning windows by spraying with a jet of water using devices of Karcher(copyright) type.
The amount of polymer introduced will generally be such that, during the use of the cleaning composition, after optional dilution, the concentration is between 0.001 g/l and 2 g/l, preferably from 0.005 g/l and 0.5 g/l.
Except when otherwise indicated, the proportions are shown by weight.
The composition for cleaning windows according to the invention comprises:
from 0.001 to 10%, preferably 0.005 to 3%, by weight of at least one water-soluble or water-dispersible copolymer as defined above;
from 0.005 to 20%, preferably from 0.5 to 10%, by weight of at least one nonionic surfactant (for example, an amine oxide) and/or anionic surfactant; and
the remainder being formed of water and/or of various additives which are common in the field.
The formulations for cleaning windows comprising said polymer can also comprise:
from 0 to 10%, advantageously from 0.5 to 5%, of amphoteric surfactant,
from 0 to 30%, advantageously from 0.5 to 15%, of solvent, such as alcohols, and the remainder being composed of water and of common additives (in particular fragrances).
The composition of the invention is also advantageous for cleaning dishes by hand or in an automatic device. In the latter case, said copolymer can be present either in the detergent formula used in the washing cycle or in the rinsing liquid.
Detergent formulations for washing dishes in automatic dishwashers advantageously comprise from 0.1 to 5%, preferably 0.2 to 3%, by weight of water-soluble or water-dispersible copolymer with respect to the total weight of dry matter of the composition.
The detergent compositions for dishwashers also comprise at least one surfactant, preferably a nonionic surfactant, in an amount ranging from 0.2 to 10%, preferably from 0.5 to 5%, of the weight of said detergent composition, expressed as dry matter, the remainder being composed of various additives and of fillers, as already mentioned above. These formulae generally comprise 30 to 95% of a builder, which builders are chosen from silicates, phosphates or carbonates. It also comprise an oxidizing system introduced at a content of between 3 and 25%.
It has been discovered, surprisingly, that the use of a copolymer according to the invention in a composition for washing in a dishwasher protects the glass and the dishes against corrosion by the washing medium during repeated washing operations.
Formulations for rinsing dishes in an automatic dishwasher advantageously comprise from 0.02 to 10%, preferably from 0.1 to 5%, by weight of copolymer with respect to the total weight of the composition.
They also comprise from 0.2 to 15%, preferably 0.5 to 5%, by weight with respect to the total weight of said composition of a surfactant, preferably a nonionic surfactant or a mixture of nonionic and anionic surfactant.
Mention may be made, among preferred nonionic surfactants, of surfactants of the following type: polyoxyethylenated C6-C12 alkylphenols, polyoxyethylenated and/or polyoxypropylenated C8-C22 aliphatic alcohols, ethylene oxide/propylene oxide block copolymers, optionally polyoxyethylenated carboxamides, and the like.
They also comprise from 0 to 40%, preferably from 3 to 30%, by weight with respect to the total weight of the composition of a calcium-sequestering organic acid, preferably citric acid.
They can also comprise an auxiliary agent of copolymer of acrylic acid and of maleic anhydride or acrylic acid homopolymers type, in a proportion of 0 to 15%, preferably 0 to 10%, by weight with respect to the total weight of said composition.
Another subject-matter of the invention is a cleaning composition for washing up dishes by hand.
Preferred detergent formulations of this type comprise from 0.1 to 5 parts by weight of copolymer of the invention per 100 parts by weight of said composition and comprise from 3 to 50, preferably from 10 to 40, parts by weight of at least one surfactant, preferably an anionic surfactant, chosen in particular from sulfates of saturated C5-C24, preferably C10-C16, aliphatic alcohols, optionally condensed with approximately 0.5 to 30, preferably 0.5 to 5, particularly 0.5 to 3, mol of ethylene oxide, in acid form or in the form of a salt, in particular an alkali metal (sodium) or alkaline earth metal (calcium, magnesium) salt, and the like.
The present invention is aimed more particularly at lathering liquid aqueous detergent formulations for washing up dishes by hand.
Said formulations can also comprise other additives, in particular other surfactants, such as:
nonionic surfactants, such as amine oxides, alkylglucamides, oxyalkylenated fatty alcohol derivatives, alkylamides or alkanolamides, amphoteric surfactants or zwitterionic surfactants,
bactericides or disinfectants, such as triclosan,
synthetic cationic polymers,
polymers for controlling the viscosity of the mixture and/or the stability of the foams formed during use,
hydrotropic agents,
hydrating or moisturizing agents or agents for protecting the skin,
dyes, fragrances, preservatives, and the like, as already mentioned above.
Another subject-matter of the invention is a cleaning composition for the external cleaning, in particular of the bodywork, of motor vehicles.
In this case also, the copolymer according to the invention can be present either in a detergent formula used for the washing operation or in a rinsing product.
The cleaning composition for motor vehicles advantageously comprises from 0.05 to 5% by weight of copolymer according to the invention with respect to the total weight of said composition, as well as:
nonionic surfactants (in a proportion of from 0 to 30%, preferably of 0.5 to 15%, of the formulation),
amphoteric and/or zwitterionic surfactants (in a proportion of 0 to 30%, preferably of 0.5 to 15%, of the formulation),
cationic surfactants (in a proportion of 0 to 30%, preferably of 0.5 to 15%, of the formulation);
anionic surfactants (in a proportion of 0 to 30%, preferably of 0.5 to 15%, of the formulation);
organic or inorganic detergency adjuvants (builders),
hydrotropic agents,
fillers, pH modifiers, and the like.
The minimum amount of surfactant present in of type of composition can be at least 1% of the formulation).
The composition of the invention is also particularly suitable for cleaning hard surfaces other than those described above, in particular ceramics (tiling, baths, sinks, and the like).
In this case, the cleaning formulation advantageously comprises from 0.02 to 5% by weight of copolymer with respect to the total weight of said composition, as well as at least one surfactant.
Preference is given, as surfactants, to nonionic surfactants, in particular the compounds produced by condensation of alkylene oxide groups as described above, which are of hydrophilic nature, with a hydrophobic organic compound, which can be of aliphatic or alkylaromatic nature.
The length of the hydrophilic chain or of the polyoxyalkylene radical condensed with any hydrophobic group can be readily adjusted in order to obtain a water-soluble compound which has the desired degree of hydrophilic/hydrophobic balance (HBL).
The amount of nonionic surfactants in the composition of the invention is generally from 0 to 30% by weight, preferably from 0 to 20% by weight.
An anionic surfactant can optionally be present in an amount of 0 to 30%, advantageously 0 to 20%, by weight.
It is also possible, but not obligatory, to add amphoteric, cationic or zwitterionic detergents to the composition of the present invention for cleaning hard surfaces.
The total amount of surfactants employed in this type of composition is generally between 1.5 and 50%, preferably between 5 and 30%, by weight and more particularly between 10 and 20% by weight, with respect to the total weight of the composition.
The composition for cleaning hard surfaces of the present invention can also comprise other minor ingredients which are cleaning additives.
For example, the composition can comprise organic or inorganic detergency adjuvants (builders) as mentioned above.
In general, the detergency adjuvant is employed in an amount of between 0.1 and 25% by weight with respect to the total weight of the composition.
Another optional ingredient in the compositions for cleaning hard surfaces of the invention is a foam modifier, which can be employed in compositions which have a tendency to produce an excess of lather during their use. An example of these materials are soaps. Soaps are fatty acid salts and comprise alkali metal, in particular the sodium or potassium salts, ammonium and alkanolammonium soaps of higher fatty acids comprising approximately from 8 to 24 carbon atoms and preferably from approximately 10 to approximately 20 carbon atoms. Particularly useful are the mono-, di- and triethanolamine salts, the sodium and potassium salts or of mixtures of fatty acids derived from coconut oil and from ground walnut oil. The amount of soap can be at least 0.005% by weight, preferably from 0.5% to 2% by weight, with respect to the total weight of the composition. Additional examples of foam modifiers are organic solvents, hydrophobic silica, silicone oil and hydrocarbons.
In addition to the ingredients mentioned above, the compositions for cleaning hard surfaces of the present invention can also comprise other optional ingredients, such as pH modifiers, dyes, optical brighteners, agents for suspending material from dirty marks, detergent enzymes, compatible bleaching agents, agents for controlling gel formation, freezing-thawing stabilizers, bactericides, preservatives, solvents, fungicides, insect repellents, hydrotropic agents, fragrances, opacifiers or pearlescent agents.
The composition of the invention can also be employed by cleaning toilet bowls.
One composition which is particularly suitable for this purpose comprises from 0.05 to 5% by weight of copolymer according to the invention.
The composition for cleaning toilet bowls according to the invention also comprises an acid cleaning agent which can comprise an inorganic acid, such as phosphoric acid, sulfamic acid, hydrochloric acid, hydrofluoric acid, sulfuric acid, nitric acid or chromic acid and mixtures thereof, or an organic acid, in particular acetic acid, hydroxyacetic acid, adipic acid, citric acid, formic acid, fumaric acid, gluconic acid, glutaric acid, glycolic acid, malic acid, maleic acid, lactic acid, malonic acid, oxalic acid, succinic acid and tartaric acid and mixtures thereof, acid salts, such as sodium bisulfate, and mixtures thereof.
The amount of acid ingredients is preferably between 0.1 to approximately 40% and preferably between 0.5 and approximately 15% by weight, with respect to the total weight of the composition.
The preferred amount depends on the type of acid cleaning agent used: for example, with sulfamic acid. It is between approximately 0.2 and approximately 1%, with hydrochloric acid between approximately 1 and approximately 5%, with citric acid between approximately 2 and approximately 10%, with formic acid between approximately 5 and approximately 15% and with phosphoric acid between approximately 5 and approximately 30%, by weight.
The amount of acid agent is generally such that the final pH of the composition is from approximately 0.5 to about 4, preferably 1 to 3.
The composition for cleaning toilet bowls also comprises from 0.5 to 10% by weight of a surfactant, so as to contribute towards removing dirty marks or so as to give foaming or wetting characteristics, or in order to increase the cleaning efficacy of the composition. The surfactant is preferably an anionic or nonionic surfactant.
Cationic surfactants can also be added to the composition for cleaning toilet bowls according to the invention in order to provide germicidal properties. A person skilled in the art will see that amphoteric surfactants can also be used. Mixtures of various surfactants can be employed, if so desired.
The composition for cleaning toilet bowls according to the invention can also comprise a thickener of gum type, in particular a xanthan gum, introduced at a concentration of 0.1 to 3%, as well as one or more of the following minor ingredients: a preservative intended to prevent the growth of microorganisms in the product, a dye, a fragrance and/or an abrasive.
The composition according to the invention is also suitable for rinsing shower walls.
The aqueous compositions for rinsing shower walls comprise from 0.02% to 5% by weight, advantageously from 0.05 to 1%, of the copolymer of the invention.
The other main active components of the aqueous compositions for rinsing showers of the present invention are at least one surfactant, present in an amount ranging from 0.5 to 5% by weight, and optionally a metal-chelating agent, present in an amount ranging from 0.01 to 5% by weight.
The preferred metal-chelating agents are ethylenediaminetetraacetic acid (EDTA) and its analogues.
The aqueous rinsing compositions for showers advantageously comprise water with, optionally, a major proportion of at least one lower alcohol and a minor proportion of additives (between approximately 0.1 and approximately 5% by weight, more advantageously between approximately 0.5% and approximately 3% by weight and even more preferably between approximately 1% and approximately 2% by weight).
Certain surfactants which can be used in this type of application are disclosed in U.S. Pat. Nos. 5,536,452 and 5,587,022, the content of which is incorporated in the present description by way of reference.
Preferred surfactants are polyethoxylated fatty esters, for example polyethoxylated sorbitan monooleates and polyethoxylated castor oil. Specific examples of such surfactants are the condensation products of 20 mol of ethylene oxide and of sorbitan monooleate (sold by Rhodia Inc. under the name Alkamuls PSMO-20(copyright) with an HLB of 15.0) and of 30 or 40 mol of ethylene oxide and of castor oil (sold by Rhodia Inc. under the name Alkamuls EL-620(copyright) (HLB of 12.0) and EL-719(copyright) (HLB of 13.6), respectively). The degree of ethoxylation is preferably sufficient to obtain a surfactant with an HLB of greater than 13. Other surfactants, such as alkylpolyglucosides, are also well suited to these compositions.
The composition according to the invention can also be employed for cleanings glass-ceramic plates.
Advantageously, the formulations for cleanings glass-ceramic plates of the invention comprise:
0.1 to 5% by weight of the copolymer of the invention;
0.1 to 1% by weight of a thickener, such as a xanthan gum;
10 to 40% by weight of an abrasive agent, such as calcium carbonate or silica;
0 to 7% by weight of a glycol, such as butyl diglycol;
1 to 10% by weight of a nonionic surfactant;
0.1 to 3% by weight of a copolymer of silicone type; and
optionally basifying agents or sequestering agents.
Another subject-matter of the invention is an aqueous biocidal cleaning composition for the treatment of hard surfaces comprising:
at least one water-soluble or water-dispersible copolymer according to the invention
at least one cationic, amphoteric or aminated, preferably cationic, biocide
and optionally at least one nonionic, amphoteric or zwitterionic, preferably nonionic, surfactant.
The biocide is preferably present in the aqueous biocidal cleaning composition at a concentration of the order of 0.1% to 20% by weight, preferably of the order of 0.5% to 5% by weight.
The copolymer according to the invention can be present in the aqueous biocidal cleaning composition at a concentration of the order of 0.01% to 20% by weight, preferably of the order of 0.05 to 5% by weight. Said copolymer does not in itself generally have a biocidal activity.
Mention may be made, among biocidal agents which may be present, of:
quaternary monoammonium salts of formulae
R1R2R3R4N+Xxe2x88x92
xe2x80x83where
R1 represents a benzyl group optionally substituted by a chlorine atom or a C1-C4 alkylbenzyl group,
R2 represents a C8-C24 alkyl group,
R3 and R4, which are alike or different, represent a C1-C4 alkyl or hydroxyalkyl group,
Xxe2x88x92 is a solubilizing anion, such as halide (for example, chloride, bromide or iodide), sulfate or methyl sulfate;
R1xe2x80x2R2xe2x80x2R3xe2x80x2R4xe2x80x2N+Xxe2x88x92
xe2x80x83where
R1xe2x80x2 and R2xe2x80x2, which are alike or different, represent a C8-C24 alkyl group,
R3xe2x80x2 and R4xe2x80x2, which are alike or different, represent a C1-C4 alkyl group,
Xxe2x88x92 is a solubilizing anion, such as halide (for example, chloride, bromide or iodide), sulfate or methyl sulfate;
xe2x80x83R1xe2x80x3R2xe2x80x3R3xe2x80x3R4xe2x80x3N+Xxe2x88x92
xe2x80x83where
R1xe2x80x3 represents a C8-C24 alkyl group,
R2xe2x80x3, R3xe2x80x3 and R4xe2x80x3, which are alike or different, represent a C1-C4 alkyl group,
Xxe2x88x92 is a solubilizing anion, such as halide (for example, chloride, bromide or iodide), sulfate or methyl sulfate; in particular:
cocoalkylbenzyldimethylammonium, (C12-C14 alkyl)benzyldimethylammonium, cocoalkyl(dichlorobenzyl)dimethylammonium, tetradecylbenzyldimethylammonium, didecyldimethylammonium or dioctyldimethylammonium chlorides,
myristyltrimethylammonium or cetyltrimethylammonium bromides;
monoquaternary heterocyclic amine salts, such as laurylpyridinium, cetylpyridinium or (C12-C14 alkyl)benzylimidazolium chlorides;
(fatty alkyl)triphenylphosphonium salts, such as myristyltriphenylphosphonium bromide;
amphoteric biocides, such as N-[Nxe2x80x2-(C8-C18 alkyl)-3-aminopropyl]glycine, N-[Nxe2x80x2-(Nxe2x80x3-(C8-C18 alkyl)-2-aminoethyl)-2-aminoethyl]glycine or N,N-bis[Nxe2x80x2-(C8-C18 alkyl)-2-aminoethyl]glycine derivatives, such as (dodecyl)(aminopropyl)glycine or (dodecyl)(diethylenediamine)glycine;
amines, such as N-(3-aminopropyl)-N-dodecyl-1,3-propanediamine.
Mention may in particular be made, among possible surfactants, of:
nonionic surfactants, such as ethylene oxide/propylene oxide block polymers, polyethoxylated sorbitan esters, sorbitan fatty esters, ethoxylated fatty esters (comprising from 1 to 25 ethylene oxide units), polyethoxylated C8-C22 alcohols (comprising from 1 to 25 ethylene oxide units), polyethoxylated C6-C22 alkylphenols (comprising from 5 to 25 ethylene oxide units), alkylpolyglycosides or amine oxides (such as (C10-C18 alkyl)dimethylamine oxides or (C8-C22 alkoxy)ethyldihydroxyethylamine oxides)
amphoteric or zwitterionic surfactants, such as C6-C20 alkyl amphoacetates or amphodiacetates (such as cocoamphoacetates), C10-C18 alkyl dimethyl betaines, C10-C18 alkyl amidopropyldimethyl betaines, C10-C18 alkyl dimethyl sulfobetaines or C10-C18 alkyl amidopropyldimethyl sulfobetaines.
These can be present in a proportion of 1 to 25%, preferably of the order of 2 to 10%, by weight of the aqueous biocidal cleaning composition.
According to the invention, in addition to the biocide and the copolymer according to the invention, which are the main constituents of the aqueous biocidal system of the invention, it is advantageously possible for other constituents to be present, such as chelating agents (for example aminocarboxylates (ethylenediaminetetraacetates, nitrilotriacetates or N,N-bis(carboxymethyl)glutamates or citrates), alcohols (ethanol, isopropanol or glycols), detergency adjuvants (phosphates or silicates), dyes, fragrances, and the like.
Said biocidal cleaning composition can be employed for disinfecting floors, walls, work surfaces, equipment, furniture, instruments, and the like in industry, the food processing field, the domestic sphere (kitchens, bathrooms, and the like) and communally.
Mention may be made, among the surfaces which can be treated, of those made of ceramic, glass, poly(vinyl chloride), formica or other hard organic polymer, stainless steel, aluminium, wood, and the like.
The cleaning and disinfecting operation consists in applying said biocidal cleaning composition, optionally diluted from 1- to 1000-fold, preferably from 1- to 100-fold, to the hard surface to be treated.
The amount of biocidal system which can be favorably employed is that corresponding to a deposition of 0.01 to 10 g, preferably of 0.1 to 1 g, of biocide per m2 of surface and to a deposition of 0.001 to 2 g, preferably of 0.01 to 0.5 g, of copolymer of the invention per m2 of surface.
Mention may be made, among the microorganisms whose proliferation can be controlled by employing the biocidal cleaning composition of the invention, of
Gram negative bacteria, such as: Pseudomonas aeruginosa; Escherichia coli; Proteus mirabilis 
Gram positive bacteria, such as: Staphylococcus aureus; Streptococcus faecium 
other bacteria which are dangerous in food, such as: Salmonella typhimurium; Listeria monocytogenes; Campylobacter jejuni; Yersinia enterocolitica 
yeasts, such as: Saccharomyces cerevisiae; Candida albicans 
fungi, such as: Aspergillus niger; Fusarium solani; Pencillium chrysogenum 
algae, such as: Chlorella saccharophilia; Chlorella emersonii; Chlorella vulgaris; Chlamydomonas eugametos. 
The biocidal system of the invention is very particularly effective against the Gram negative microorganism Pseudomonas aeroginosa, the Gram positive microorganism Staphylococcus aureus or the fungus Aspergillus niger. 
Another subject-matter of the invention is the use of a water-soluble or water-dispersible copolymer as defined above in the cleaning or rinsing of a hard surface, in particular in order to confer hydrophilization properties on a hard surface.
The hydrophilization properties conferred by the copolymer of the invention are in particular properties of xe2x80x9cresistance to runningxe2x80x9d, xe2x80x9cresistance to condensationxe2x80x9d, xe2x80x9cresistance to stainsxe2x80x9d and/or xe2x80x9cresistance to marksxe2x80x9d.
A subject-matter of the invention is likewise a process for improving the hydrophilicity of a hard surface by treating said surface using a cleaning composition comprising at least one copolymer according to the invention.
Another subject-matter of the invention is the use of a copolymer as defined above for decreasing the rate of drying of a hard surface to which the copolymer is applied.
Another subject-matter of the invention is the use, in a detergent composition for washing dishes in an automatic dishwasher, of a copolymer according to the invention as agent for eliminating or decreasing the corrosion of the glass and of the designs present on the glass or the dishes during repeated washing operations.
Finally, a subject-matter of the invention is a process for protecting the glass, dishes and designs by washing the glass and dishes in an automatic dishwasher using a cleaning composition comprising at least one copolymer according to the invention.